Salts of lewis acid/acid adducts and catalyst activators therefrom

ABSTRACT

A compound useful as a cocatalyst or cocatalyst component, especially for use as an addition polymerization catalyst compound, corresponding to the formula: (A* +a ) b (Z*J* j ) −c   d , wherein:  
     A* is a proton or a cation of from 1 to 80 atoms, preferably 1 to 60 atoms, not counting hydrogen atoms, said A* having a charge +a;  
     Z* is an anion group of from 1 to 50 atoms, preferably 1 to 30 atoms, not counting hydrogen atoms, further containing two or more Lewis base sites, said Z* being the conjugate base of an inorganic Bronsted acid or a carbonyl- or non-cyclic, imino-group containing organic Bronsted acid;  
     J* independently each occurrence is a Lewis acid of from 1 to 80 atoms, preferably 1 to 60 atoms, not counting hydrogen atoms, coordinated to at least one Lewis base site of Z*, and optionally two or more such J* groups may be joined together in a moiety having multiple Lewis acidic functionality;  
     j is a number from 1 to 12; and  
     a, b, c, and d are integers from 1 to 3, with the proviso that a×b is equal to c×d.

CROSS REFERENCE STATEMENT

[0001] This application claims the benefit of U.S. ProvisionalApplication No. 60/307,249, filed Jul. 23, 2001.

BACKGROUND INFORMATION

[0002] The present invention relates to compounds that are useful ascatalyst components. More particularly the present invention relates tosuch compounds that are particularly adapted for use in the coordinationpolymerization of unsaturated compounds comprising an anion containingat least two Lewis basic sites derived from certain inorganic or organicBronsted acids, which are coordinated to Lewis acids. Such compounds areparticularly advantageous for use in forming supported polymerizationcatalysts wherein at least the catalyst activator is chemically attachedto a substrate material.

[0003] It is previously known in the art to activate Ziegler-Nattapolymerization catalysts, particularly such catalysts comprising Group3-10 metal complexes containing delocalized π-bonded ligand groups, bythe use of Bronsted acid salts capable of transferring a proton to forma cationic derivative or other catalytically active derivative of suchGroup 3-10 metal complex. Preferred Bronsted acid salts are suchcompounds containing a cation/anion pair that is capable of renderingthe Group 3-10 metal complex catalytically active. Suitable activatorscomprise fluorinated arylborate anions, such astetrakis(pentafluorophenyl)borate. Additional suitable anions includesterically shielded diboron anions of the formula:

[0004] wherein:

[0005] S is hydrogen, alkyl, fluoroalkyl, aryl, or fluoroaryl, Ar^(F) isfluoroaryl, and X¹ is either hydrogen or halide, disclosed in U.S. Pat.No. 5,447,895. Additional examples include carborane compounds such asare disclosed and claimed in U.S. Pat. No. 5,407,884.

[0006] Examples of preferred charge separated (cation/anion pair)activators are ammonium, sulfonium, or phosphonium salts capable oftransferring a hydrogen ion, disclosed in U.S. Pat. Nos. 5,198,401,5,132,380, 5,470,927 and 5,153,157, as well as oxidizing salts such asferrocenium, silver or lead salts, disclosed in U.S. Pat. Nos. 5,189,192and 5,321,106 and strongly Lewis acidic salts such as carbonium orsilylium salts, disclosed in U.S. Pat. Nos. 5,350,723 and 5,625,087.

[0007] Further suitable activators for the above metal complexes includestrong Lewis acids including tris(perfluorophenyl)borane andtris(perfluorobiphenyl)borane. The former composition has beenpreviously disclosed for the above stated end use in EP-A-520,732,whereas the latter composition is similarly disclosed by Marks, et al.,in J. Am. Chem. Soc., 118, 12451-12452 (1996).

[0008] In WO99/42467, WOO 1/23442 and WO02/08303 expanded ionic catalystactivators are disclosed that are well suited for use as olefinpolymerization activators.

[0009] Despite the satisfactory performance of the foregoing catalystactivators under a variety of polymerization conditions, there is stilla need for improved cocatalysts for use in the activation of variousmetal complexes especially under a variety of reaction conditions.Accordingly, it would be desirable if there were provided compounds thatcould be employed in solution, slurry, gas phase or high pressurepolymerizations and under homogeneous or heterogeneous processconditions having improved activation properties.

SUMMARY OF THE INVENTION

[0010] According to the present invention there are now providedcompounds useful as catalyst activators corresponding to the formula:(A*^(+a))_(b)(Z*J* _(j))^(−c) _(d),

[0011] wherein:

[0012] A* is a proton or a cation of from 1 to 80 atoms, preferably 1 to60 atoms, not counting hydrogen atoms, said A* having a charge +a,

[0013] Z* is an anion group of from 1 to 50 atoms, preferably 1 to 30atoms, not counting hydrogen atoms, further containing two or more Lewisbase sites, said Z* being the conjugate base of an inorganic Bronstedacid or a carbonyl- or non-cyclic, imino-group containing organicBronsted acid;

[0014] J* independently each occurrence is a Lewis acid of from 1 to 80atoms, preferably 1 to 60 atoms, not counting hydrogen atoms,coordinated to at least one Lewis base site of Z*, and optionally two ormore such J* groups may be joined together in a moiety having multipleLewis acidic functionality;

[0015] j is a number from 1 to 12; and

[0016] a, b, c, and d are integers from 1 to 3, with the proviso thata×b is equal to c×d.

[0017] The foregoing compounds may be utilized in combination with oneor more Group 3-10 or Lanthanide metal complexes to form catalystcompositions for polymerization of addition polymerizable monomers,especially ethylenically unsaturated monomers, most preferably,C_(2-20,000) α-olefins. Additionally, the compounds may be utilized toform latent activators, that is, compounds that may themselves not causea metal complex to become catalytically active due, for example, to thepresence of a reactive group such as a hydroxyl group, but which may beconverted to an active compound by, for example, in-situ reaction of thehydroxyl group with a Lewis acid, especially an aluminum hydrocarbylcompound, or an alkali metal halide or ammonium halide salt. Moreover,such compounds may be deposited onto solid supports, such as byimpregnation, surface deposition, physisorption or chemical reactionwith the support, reactive functionality of the support, or chemicalmodifiers associated with the support, to form heterogeneous catalystcomponents for use in preparing heterogeneous catalyst compositions foruse in polymerization of the foregoing monomers.

[0018] Thus, in one embodiment of the invention, the foregoing compoundscontaining hydroxyl or other reactive functionality are used to formsupported catalyst components by reaction of the hydroxyl group thereofwith reactive functionality of a support material, or by conversion ofthe dialkylaluminumoxyhydrocarbyl, trihydrocarbylsiloxyhydrocarbyl orhydrocarbyloxyhydrocarbyl group to a reactive functionality and reactionthereof with reactive functionality of a support material. The resultingsupported catalyst components are highly resistant to loss of activatorcompound in a liquid reaction medium such as occurs in a slurrypolymerization. One or more Group 3-10 or Lanthanide metal complexes,preferably a Group 4 metal complex, and additional additives, modifiersand adjuvants may be added to the catalyst component, either before,after or simultaneous with addition of the cocatalyst of the presentinvention, to form the fully formulated catalyst composition.Accordingly, in one embodiment of the invention the foregoing structurescan be created on a surface containing chemically or physically bondedanionic groups, Z*.

[0019] Another embodiment of the invention is a composition of mattercomprising the admixture or reaction product, optionally in an inertdiluent, of an inorganic Bronsted acid or a carbonyl- or non-cyclic,imino-group-containing organic Bronsted acid; from one to twelve molesper mole of Bronsted acid of a Lewis acid having from 1 to 80,preferably 1 to 60 atoms, not counting hydrogen atoms; optionally aLewis base of from 1 to 80, preferably 1 to 60 atoms, not countinghydrogen, preferably an amine or phosphine containing Lewis base; andfurther optionally an organoaluminum compound, preferably an alumoxane,especially methylalumoxane or modified methylalumoxane.

[0020] Additionally according to the present invention there is provideda catalyst composition for polymerization of an ethylenicallyunsaturated, polymerizable monomer comprising, in combination, the abovedescribed activator compound or composition of matter, a Group 3-10metal complex that is capable of activation to form an additionpolymerization catalyst, or the reaction product of such combination,and optionally a support.

[0021] Additionally according to the present invention there is provideda process for polymerization of one or more ethylenically unsaturated,polymerizable monomers comprising contacting the same, optionally in thepresence of an inert aliphatic, alicyclic or aromatic hydrocarbon, withthe above catalyst compositions or supported catalyst compositions.

[0022] The foregoing compounds are uniquely adapted for use inactivation of a variety of metal complexes, especially Group 4 metalcomplexes, under standard and a typical olefin polymerizationconditions. Because of this fact, the foregoing compounds are capable offorming highly desirable olefin polymers in high efficiency. Especiallydesirably, the compounds are readily hydrolyzed and are easily removedfrom the polymer product after polymerization.

DETAILED DESCRIPTION OF THE INVENTION

[0023] All references herein to elements belonging to a certain Grouprefer to the Periodic Table of the Elements published and copyrighted byCRC Press, Inc., 1999. Also any reference to the Group or Groups shallbe to the Group or Groups as reflected in this Periodic Table of theElements using the IUPAC system for numbering groups. For purposes ofUnited States patent practice, the contents of any patent, patentapplication or publication referenced herein are hereby incorporated byreference in their entirety herein, especially with respect to thedisclosure of structures, synthetic techniques and general knowledge inthe art. The term “comprising” and derivatives thereof, when used hereinwith respect to a composition, mixture, or sequence of steps, is notintended to exclude the additional presence of any other compound,component or event.

[0024] The catalyst activators of the invention are furthercharacterized in the following manner. A*^(+a) is desirably chosen toprovide overall neutrality to the compound and to not interfere withsubsequent catalytic activity. Moreover, the cation may participate inthe formation of the active catalyst species, desirably through a protontransfer, oxidation, or ligand abstraction mechanism, or a combinationthereof. Additionally, certain cations beneficially improve thesolubility of the resulting activator in particular reaction media underuse conditions. For example, in the homopolymerization orcopolymerization of aliphatic olefins, particularly in the solutionphase, an aliphatic diluent is commonly used. Accordingly, cationicspecies that are relatively soluble in such reaction media, or renderthe catalyst activator more soluble therein are highly preferred.

[0025] Examples of suitable cations include: ammonium, sulfonium,phosphonium, oxonium, carbonium, and silylium cations, preferably thosecontaining up to 80 atoms not counting hydrogen, a proton, as well asferrocenium, Ag⁺, Pb⁺², or similar oxidizing cations. In a preferredembodiment, a, b, c and d are all equal to one.

[0026] Preferred A*^(+a) cations are protons, and ammonium cations,especially trihydrocarbyl-substituted ammonium cations. Examples includetrimethylammonium-, triethylammonium-, tripropylammonium-,tri(n-butyl)ammonium-, methyldi(C₁₄₋₁₈ alkyl)ammonium-, dimethyl(C₁₄₋₁₈alkyl)ammonium-, N,N-dimethylanilinium-, N,N-diethylanilinium-,N,N-dimethyl(2,4,6-trimethylanilinium)-, N,N-di(tetradecyl)lanilinium-,N,N-di(tetradecyl)-2,4,6-trimethylanilinium)-,N,N-di(octadecyl)lanilinium-,N,N-di(octadecyl)-2,4,6-trimethylanilinium)-, andmethyldicyclohexylammonium-cations.

[0027] More preferred cations include those containing one or twoC₁₀-C₄₀ alkyl groups, such as methylbis(octadecyl)ammonium-,dimethyloctadecylammonium-, methylbis(tetradecyl)ammonium-,bis(octadecyl)anilinium-, andbis(octadecyl)-3,5-dimethylanilinium-cations. It is further understoodthat the cation may comprise a mixture of hydrocarbyl groups ofdiffering lengths. For example, the protonated ammonium cation derivedfrom the commercially available long chain amine comprising a mixture oftwo C₁₄, C₁₆ or C₁₈ alkyl groups and one methyl group. Such amines areavailable from Witco Corp., under the trade name Kemamine™ T9701, andfrom Akzo-Nobel under the trade name Armeen™ M2HT.

[0028] Preferably Z* is the conjugate base of an inorganic acid and isselected from the group consisting of: NO₃ ⁻, PO₄ ^(3−,)SO₄ ²⁻, RSO₃ ⁻and CO₃ ²⁻, or Z* is the conjugate base of an organic acid and isselected from the group consisting of: [RC(O)O]⁻, [RC(NR)NR]⁻,[R′C(O)CRC(O)R′]⁻, [(R′C(O))₃C]⁻, [RC(NR)CRC(NR)R]⁻, and [(RC(NR))₃C]⁻,

[0029] wherein each R is independently a hydrogen-; hydrocarbyl-; orhalocarbyl-group; a hydrocarbyl group further substituted with one ormore carbonyl-, halo-, hydroxy-, dialkylamino-, dialkylaluminumoxy-,trihydrocarbylsilyl-, trihydrocarbylsiloxy-, or hydrocarbyloxy-groups;or a halocarbyl group further substituted with one or more carbonyl-,hydroxy-, dialkylamino-, dialkylaluminumoxy-, trihydrocarbylsilyl-,trihydrocarbylsiloxy-, or hydrocarbyloxy-groups; and each R′ isindependently R or two R′ groups may be joined together thereby forminga divalent group.

[0030] More preferably, Z* is an acetylacetonate, cyclohexa-1,3-dionate,[RC(O)O]⁻ or NO₃ ⁻, wherein R is a C₆₋₂₄ hydrocarbyl group, mostpreferably a C₁₂₋₂₄ alkyl group, or the conjugate base anion derivedfrom indane-1,3-dione or methyltriacetyl corresponding to the followingstructure:

[0031] Coordinated to some or all of the Lewis base sites of the Z*anion, that is, to the oxygen or nitrogen atoms, are from 1 to 12 Lewisacids, J*, two or more of which may be joined together in a moietyhaving multiple Lewis acidic functionality. Each J* group or when two ormore J* groups are joined together, the resulting combination, is aneutral compound. Optionally, said J* group may comprise a hydroxylgroup or a polar group containing quiescent reactive functionality, solong as such functionality does not interfere with the Lewis acidfunctionality thereof. Preferably, from 2 to 4 J* groups having from 3to 100 atoms not counting hydrogen are present in each compound of theinvention.

[0032] More specific examples of the foregoing Lewis acid compounds, J*,correspond to the formula:

[0033] wherein:

[0034] M* is aluminum, gallium or boron;

[0035] R¹ and R² independently each occurrence are hydride, halide, or ahydrocarbyl, halocarbyl, halohydrocarbyl, dialkylamido, alkoxide, oraryloxide group of up to 20 carbons, optionally substituted with ahydroxyl group or a polar group containing quiescent reactivefunctionality, and

[0036] Ar^(f1)-Ar^(f2) in combination, independently each occurrence, isa divalent fluoro-substituted aromatic group of from 6 to 20 carbons,optionally substituted with a hydroxyl group or a polar group containingquiescent reactive functionality.

[0037] Highly preferred Lewis acids are aluminum or boron compoundscorresponding to the formula: AIR¹ ₃, or BR¹ ₃, wherein R¹ independentlyeach occurrence is selected from hydrocarbyl, halocarbyl, andhalohydrocarbyl radicals, or such groups further substituted with ahydroxyl group or a polar group containing quiescent reactivefunctionality, said R¹ having up to 20 carbons. In a more highlypreferred embodiment, R¹ is a C₆₋₂₀ aryl group or a fluorinated C₁₋₂₀hydrocarbyl group, most preferably, a fluorinated aryl group,especially, pentafluorophenyl.

[0038] Preferred examples of the foregoing Lewis acid groups containingmultiple Lewis acid sites are:

[0039] By the term “polar group containing quiescent reactivefunctionality” is meant an oxygen, nitrogen, sulfur, or phosphoruscontaining ligand group that is capped or protected and thereby renderedrelatively inert to reaction conditions used in the synthesis or use ofthe present compounds, but wherein the capping or protecting groups maybe later removed, if desired, thereby generating a reactive polarfunctional group, especially a hydroxyl group or metallated derivativethereof., Suitable reactive polar functional groups include hydroxyl,thiol, amine, and phosphine groups, or hydrocarbyl-, alkali metal- orBronsted acid salt-derivatives thereof. Suitable quiescent reactivefunctionality includes the trihydrocarbyllsilyl-, trihydrocarbylgermyl-,dihydrocarbylaluminum-, hydrocarbylzinc- orhydrocarbylmagnesium-functionalized derivative of the foregoing polargroups. Particularly preferred polar containing quiescent reactivefunctional groups are trihydrocarbylsiloxy,trihydrocarbylsiloxy-substituted hydrocarbyl, dihydrocarbylaluminoxy anddihydrocarbylaluminoxy substituted hydrocarbyl groups. Especiallypreferred are the trialkylsiloxy- or dialkylaluminoxy-derivatives ofsuch polar functional groups, containing from 1 to 6 carbon in eachalkyl group. Especially preferred quiescent reactive functional groupsare trimethylsiloxy-groups and diethylaluminoxy-groups.

[0040] Such polar group containing quiescent reactive functionality isactivated by reaction with a metal hydrocarbyl-, metal halocarbyl-,hydrocarbylmetaloxy- or metal halohydrodarbyl-compound under ligandexchange conditions, thereby producing a neutral hydrocarbon,halohydrocarbon, trimethylsilylhydrocarbon,trimethylsilylhalo-hydrocarbon or trimethylsilylhalocarbon compound as aby-product. The hydroxyl group or polar group containing quiescentreactive functionality may also be employed to react with hydroxyl-,alkylmetal-, hydrocarbylsilyl-, or hydrocarbylsiloxy-functionality of asolid, particulated, support material, optionally after conversion to ametallated or protonated intermediate. This results in tethering orchemically attaching the activator to the surface of the solid,particulated, support material. The resulting substance demonstratesenhanced resistance to loss or removal when exposed to liquids in apolymerization process.

[0041] In a preferred embodiment, the foregoing hydroxyl group or polargroup containing quiescent reactive functionality is located in the Z*ligand. Examples include hydroxyl, trialkylsiloxy-,trialkylsiloxyalkyl-, trialkylsiloxyaryl-, anddialkylaluminoxyaryl-substituted derivatives of carboxylic acids.

[0042] Especially suitable compounds according to the present inventioninclude the tris(pentafluorophenyl)borane-coordinated derivatives ofammonium-, phosphonium-, sulfonium-, oxonium-, carbonium-, silylium-,lead (II)-, silver- or ferrocenium-carboxylates, acetylacetonates,cyclohexa-1,3-dionates or nitrates. Preferred compounds are the ammoniumsalts, especially those which comprise trihydrocarbyl-substitutedammonium cations, especially trimethylammonium-, triethylammonium-,tripropylammonium-, tri(n-butyl)ammonium-, methyldi(octadecyl)ammonium-,methyldi(tetradecyl)ammonium-, methyl(tetradecyl)(octadecyl)ammonium-,N,N-dimethylanilinium-, N,N-diethylanilinium-,N,N-dimethyl(2,4,6-trimethylanilinium)-, N,N-di(tetradecyl)lanilinium-,N,N-di(tetradecyl)-2,4,6-trimethylanilinium)-,N,N-di(octadecyl)lanilinium-,N,N-di(octadecyl)-2,4,6-trimethylanilinium)-, andmethyldicyclohexylammonium-cations, or mixtures thereof.

[0043] Most preferred ammonium cation containing salts are thosecontaining trihydrocarbyl-substituted ammonium cations containing one ortwo C₁₀-C₄₀ alkyl groups, especially methylbis(octadecyl)ammonium- andmethylbis(tetradecyl)ammonium-cations. It is further understood that thecation may comprise a mixture of hydrocarbyl groups of differinglengths. For example, the protonated ammonium cation derived from thecommercially available long chain amine comprising a mixture of two C₁₄,C₁₆ or C₁₈ alkyl groups and one methyl group. Such amines are availablefrom Witco Corp., under the trade name Kemamine™ T9701, and fromAkzo-Nobel under the trade name Armeen™ M2HT.

[0044] Most preferred cocatalysts according to the present invention arethe mono- and bis(tris(pentafluorophenyl)borane)-coordinated derivativesof trihydrocarbylammonium stearates, 1,3-cylcohexadionates oracetylacetonates, most especiallybis(tris(pentafluorophenyl)borane)-coordinated derivatives ofmethyldioctyldecylammonium stearate, methylditetradecylammoniumstearate, or mixtures thereof, and thebis(tris(pentafluorophenyl)borane)-coordinated derivatives of a reactionproduct formed by contacting of a trihydrocarbylamine with1,3-cylcohexadione or acetylacetone, or mixtures thereof, such as thebis(tris(pentafluorophenyl)borane)-coordinated derivatives of a reactionproduct formed by contacting methyldioctyldecylamine,methylditetradecylamine, or a mixture thereof with 1,3-cylcohexadione,acetylacetone, or a mixture thereof.

[0045] The compounds may be prepared by simply combining the Lewis acid,J*, or its Lewis base adduct, such as an ethereate, with the neutralcompound corresponding to the cation/anion complex,(A*^(+a))_(b)(Z*)^(−c) _(d), or the reaction mixture resulting fromcontacting a Lewis base, such as an amine, with the Bronsted acid HZ*.They may also be prepared by combination in any order of the Lewis acid,J*, or its Lewis base adduct, such as an etherate, with the protonatedversion of the conjugated base of the Bronsted acid, HZ*, and optionallya Lewis base, such as an amine, derived from A*^(+a). Additionally, theymay be prepared by a condensation reaction between a metal salt of theanion, Z*, and a Lewis acid, J*, preferably under phase transferconditions, using for example a crown ether to solubilize the metal saltif necessary, followed by a metathesis reaction with the correspondinghalide salt of the cation, A*^(+a). Addition of the free basecorresponding to the cation, A*^(+a), results in formation of the chargeseparated species, which may be recovered from the reaction mixture bydevolatilization or used without further purification. Finally, they mayalso be prepared by reaction of a metal salt, especially a silver saltof the anion, Z* with the corresponding halide salt of the cation,A*^(+a). Addition of the neutral Lewis acid, J, results in formation ofthe desired product.

[0046] If a hydroxyl group or quiescent reactive functionality ispresent in the compounds of the present invention, or reactivederivatives thereof, they may be readily attached to a reactivesubstrate, such as a particulated solid containing reactive hydrocarbylgroups, especially hydrocarbylmetal- orhydrocarbylmetalloid-functionality. Examples include alumina, silica,aluminosilicates, and aluminum magnesium silicate materials, containingreactive hydroxyl- or hydrocarbyl-functionality, and such materialstreated with any substance to impart reactive metal-hydrocarbyl ormetalloid-hydrocarbyl functionality. Examples of such treatingsubstances include trihydrocarbyl aluminum compounds, chlorosilanecompounds, and mono- or di-hydrocarbylsilane compounds that react with aportion or all of reactive surface hydroxyl functionality of thesubstrate to form a “capped” derivative. This technique is known in theart and disclosed for example in U.S. Pat. No. 6,087,293.

[0047] Suitable catalysts for use in combination with the foregoingcocatalysts include any compound or complex of a metal of Groups 3-10 ofthe Periodic Table of the Elements capable of being activated topolymerize ethylenically unsaturated compounds by the presentactivators. Examples include Group 10 diimine derivatives correspondingto the formula:

[0048] wherein

[0049] M* is Ni(II) or Pd(II);

[0050] K′ is halo, hydrocarbyl, or hydrocarbyloxy;

[0051] and the two nitrogen atoms are linked by a bridging system.

[0052] Such catalysts have been previously disclosed in J. Am. Chem.Soc., 118, 267-268 (1996), J. Am. Chem. Soc., 117,6414-6415 (1995), andOrganometallics, 16, 1514-1516, (1997).

[0053] Additional catalysts include derivatives of Group 3, 4, orLanthanide metals which are in the +2, +3, or +4 formal oxidation state.Preferred compounds include metal complexes containing from 1 to 3π-bonded anionic or neutral ligand groups, which may be cyclic ornon-cyclic delocalized π-bonded anionic ligand groups. Exemplary of suchπ-bonded anionic ligand groups are conjugated or nonconjugated, cyclicor non-cyclic dienyl groups, allyl groups, boratabenzene groups,phosphole, and arene groups. By the term “π-bonded” is meant that theligand group is bonded to the transition metal by a sharing of electronsfrom a partially delocalized π-bond.

[0054] Each atom in the delocalized it-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substitutedmetalloid radicals wherein the metalloid is selected from Group 14 ofthe Periodic Table of the Elements, and such hydrocarbyl- orhydrocarbyl-substituted metalloid radicals further substituted with aGroup 15 or 16 hetero atom containing moiety. Included within the term“hydrocarbyl” are C₁₋₂₀ straight, branched and cyclic alkyl radicals,C₆₋₂₀ aromatic radicals, C₇₋₂₀ alkyl-substituted aromatic radicals, andC₇₋₂₀ aryl-substituted alkyl radicals. In addition two or more suchradicals may together form a fused ring system, including partially orfully hydrogenated fused ring systems, or they may form a metallocyclewith the metal. Suitable hydrocarbyl-substituted organometalloidradicals include mono-, di- and tri-substituted organometalloid radicalsof Group 14 elements wherein each of the hydrocarbyl groups containsfrom 1 to 20 carbon atoms. Examples of suitable hydrocarbyl-substitutedorganometalloid radicals include trimethylsilyl, triethylsilyl,ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, andtrimethylgermyl groups. Examples of Group 15 or 16 hetero atomcontaining moieties include amine, phosphine, ether or thioethermoieties or divalent derivatives thereof, e.g. amide, phosphide, etheror thioether groups bonded to the transition metal or Lanthanide metal,and bonded to the hydrocarbyl group or to the hydrocarbyl-substitutedmetalloid containing group.

[0055] Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,phosphole, and boratabenzene groups, as well ashydrocarbyl-silyl-(including mono-, di-, or tri(hydrocarbyl)silyl)substituted derivatives thereof. Preferred anionic, delocalizedit-bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl,tetramethylcyclopentadienyl,tetramethyl(trimethylsilyl)-cyclopentadienyl, indenyl,2,3-dimethylindenyl, fluorenyl, 2-methylindenyl,2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, andtetrahydroindenyl.

[0056] The boratabenzenes are anionic ligands that are boron containinganalogues to benzene. They are previously known in the art having beendescribed by G. Herberich, et al., in Organometallics, 14,1, 471-480(1995). Preferred boratabenzenes correspond to the formula:

[0057] wherein R″ is selected from the group consisting of hydrocarbyl,silyl, N,N-dihydrocarbylamino, or germyl, said R″ having up to 20non-hydrogen atoms. In complexes involving divalent derivatives of suchdelocalized π-bonded groups one atom thereof is bonded by means of acovalent bond or a covalently bonded divalent group to another atom ofthe complex thereby forming a bridged system.

[0058] Phospholes are anionic ligands that are phosphorus containinganalogues to a cyclopentadienyl group. They are previously known in theart having been described by WO 98/50392, and elsewhere. Preferredphosphole ligands correspond to the formula:

[0059] wherein R″ is selected from the group consisting of hydrocarbyl,silyl, N,N-dihydrocarbylamino, or germyl, said R″ having up to 20non-hydrogen atoms, and optionally one or more R″ groups may be bondedtogether forming a multicyclic fused ring system, or form a bridginggroup connected to the metal. In complexes involving divalentderivatives of such delocalized π-bonded groups one atom thereof isbonded by means of a covalent bond or a covalently bonded divalent groupto another atom of the complex thereby forming a bridged system.

[0060] Phosphinimine/cyclopentadienyl complexes are disclosed inEP-A-89058 1 and correspond to the formula [R* **)₃—P═N]_(b)M**(Cp)(L¹)_(3-b), wherein:

[0061] R*** is a monovalent ligand, illustrated by hydrogen, halogen, orhydrocarbyl, or two R*** groups together form a divalent ligand,

[0062] M** is a Group 4 metal,

[0063] Cp is cyclopentadienyl, or similar delocalized π-bonded group,

[0064] L¹ is a monovalent ligand group, illustrated by hydrogen, halogenor hydrocarbyl,

[0065] b is a number from 1 to 3; and

[0066] n is 1 or 2.

[0067] A suitable class of catalysts are transition metal complexescorresponding to the formula:

Lp₁MX_(m)X′_(n)X″_(p), or a dimer thereof

[0068] wherein:

[0069] Lp is an anionic, delocalized, π-bonded group that is bound to M,containing up to 50 non-hydrogen atoms, optionally two Lp groups may bejoined together forming a bridged structure, and further optionally oneLp may be bound to X;

[0070] M is a metal of Group 4 of the Periodic Table of the Elements inthe +2, +3 or +4 formal oxidation state;

[0071] X is an optional, divalent group of up to 50 non-hydrogen atomsthat together with Lp forms a metallocycle with M;

[0072] X′ is an optional neutral ligand having up to 20 non-hydrogenatoms;

[0073] X″ each occurrence is a monovalent, anionic moiety having up to40 non-hydrogen atoms, optionally, two X″ groups may be covalently boundtogether forming a divalent dianionic moiety having both valences boundto M, or, optionally 2 X″ groups may be covalently bound together toform a neutral, conjugated or nonconjugated diene that is π-bonded to M(whereupon M is in the +2 oxidation state), or further optionally one ormore X″ and one or more X′ groups may be bonded together thereby forminga moiety that is both covalently bound to M and coordinated thereto bymeans of Lewis base functionality;

[0074] 1 is 0, 1 or 2;

[0075] m is 0 or 1;

[0076] n is a number from 0 to 3;

[0077] p is an integer from 0 to 3; and

[0078] the sum, l+m+p, is equal to the formal oxidation state of M,except when 2 X″ groups together form a neutral conjugated ornon-conjugated diene that is π-bonded to M, in which case the sum l+m isequal to the formal oxidation state of M.

[0079] Preferred complexes include those containing either one or two Lpgroups. The latter complexes include those containing a bridging grouplinking the two Lp groups. Preferred bridging groups are thosecorresponding to the formula (ER*₂)_(x), B(NR**₂), or B(NR**₂)₂, whereinE is silicon, germanium, tin, or carbon, R* independently eachoccurrence is hydrogen or a group selected from silyl, hydrocarbyl,hydrocarbyloxy, and combinations thereof, said R* having up to 30 carbonor silicon atoms, R** independently each occurrence is a group selectedfrom silyl, hydrocarbyl, and combinations thereof, said R** having up to30 carbon or silicon atoms, and x is 1 to 8. Preferably, R*independently each occurrence is methyl, ethyl, propyl, benzyl, butyl,phenyl, methoxy, ethoxy, or phenoxy, and R** is methyl, ethyl, propyl,benzyl or butyl.

[0080] Examples of the complexes containing two Lp groups are compoundscorresponding to the formula:

[0081] wherein:

[0082] M is titanium, zirconium or hafnium, preferably zirconium orhafnium, in the +2 or +4 formal oxidation state;

[0083] R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system, and

[0084] X″ independently each occurrence is an anionic ligand group of upto 40 non-hydrogen atoms, or two X″ groups together form a divalentanionic ligand group of up to 40 non-hydrogen atoms or together are aconjugated diene having from 4 to 30 non-hydrogen atoms forming aπ-complex with M, whereupon M is in the +2 formal oxidation state, and

[0085] R*, R**, E and x are as previously defined, preferably (ER*₂)_(x)is dimethylsilandiyl or ethylene, and BNR**₂ isdi(isopropyl)aminoborandiyl.

[0086] The foregoing metal complexes are especially suited for thepreparation of polymers having stereoregular molecular structure. Insuch capacity it is preferred that the complex possesses C_(s) symmetryor possesses a chiral, stereorigid structure. Examples of the first typeare compounds possessing different delocalized π-bonded systems, such asone cyclopentadienyl group and one fluorenyl group. Similar systemsbased on Ti(IV) or Zr(IV) were disclosed for preparation of syndiotacticolefin polymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256(1980). Examples of chiral structures include rac bis-indenyl complexes.Similar systems based on Ti(IV) or Zr(IV) were disclosed for preparationof isotactic olefin polymers in Wild et al., J. Organomet. Chem., 232,233-47, (1982).

[0087] Exemplary bridged ligands containing two π-bonded groups are:dimethylbis(cyclopentadienyl)silane,dimethylbis(tetramethylcyclopentadienyl)silane,dimethylbis(2-ethylcyclopentadien-1-yl)silane,dimethylbis(2-t-butylcyclopentadien-1-yl)silane,2,2-bis(tetramethylcyclopentadienyl)propane,dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane,dimethylbis(fluoren-1-yl)silane,dimethylbis(tetrahydrofluoren-1-yl)silane,dimethylbis(2-methyl-4-phenylinden-1-yl)-silane,dimethylbis(2-methylinden-1-yl)silane,di(isopropyl)aminobis(cyclopentadien-1-yl)borandiyl,di(isopropyl)aminobis(2-methyl4-phenylinden-1-yl)-borandiyl,di(isopropyl)aminobis(2-methylinden-1-yl)borandiyl,dimethyl(cyclopentadienyl)(fluoren-1-yl)silane,dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane,dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane, (1, 1, 2,2-tetramethy)-1, 2-bis(cyclopentadienyl)disilane, (1,2-bis(cyclopentadienyl)ethane, anddimethyl(cyclopentadienyl)-1-(fluoren-1-yl)methane.

[0088] Preferred X″ groups are selected from hydride, hydrocarbyl,silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl andaminohydrocarbyl groups, or two X″ groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Most preferred X″ groups are C₁₋₂₀hydrocarbyl groups.

[0089] Complexes containing two Lp groups including bridged complexessuitable for use in the present invention include:

[0090] bis(cyclopentadienyl)zirconiumdimethyl,

[0091] bis(cyclopentadienyl)zirconium dibenzyl,

[0092] bis(cyclopentadienyl)zirconium methyl benzyl,

[0093] bis(cyclopentadienyl)zirconium methyl phenyl,

[0094] bis(cyclopentadienyl)zirconiumdiphenyl,

[0095] bis(cyclopentadienyl)titanium-allyl,

[0096] bis(cyclopentadienyl)zirconiummethylmethoxide,bis(cyclopentadienyl)zirconiummethylchloride,

[0097] bis(pentamethylcyclopentadienyl)zirconiumdimethyl,

[0098] bis(pentamethylcyclopentadienyl)titaniumdimethyl,

[0099] bis(indenyl)zirconiumdimethyl,

[0100] indenylfluorenylzirconiumdimethyl,

[0101] bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl),

[0102] bis(indenyl)zirconiummethyltrimethylsilyl,

[0103] bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl,

[0104] bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl,

[0105] bis(pentamethylcyclopentadienyl)zirconiumdibenzyl,

[0106] bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide,

[0107] bis(pentamethylcyclopentadienyl)zirconiummethylchloride,

[0108] bis(methylethylcyclopentadienyl)zirconiumdimethyl,

[0109] bis(butylcyclopentadienyl)zirconiumdibenzyl,

[0110] bis(t-butylcyclopentadienyl)zirconiumdimethyl,

[0111] bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl,

[0112] bis(methylpropylcyclopentadienyl)zirconiumdibenzyl,

[0113] bis(trimethylsilylcyclopentadienyl)zirconiumdibenzyl,

[0114] dimethylsilyl-bis(cyclopentadienyl)zirconiumdimethyl,

[0115] dimethylsilyl-bis(tetramethylcyclopentadienyl)titanium (III)allyl

[0116] dimethylsilyl-bis(t-butylcyclopentadienyl)zirconiumdibenzyl,

[0117] dimethylsilyl-bis(n-butylcyclopentadienyl)zirconiumbis(trimethylsilyl),(methylene-bis(tetramethylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,(methylene-bis(n-butylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,

[0118] dimethylsilyl-bis(indenyl)zirconiumbenzylchloride,

[0119] dimethylsilyl-bis(2-methylindenyl)zirconiumdimethyl,

[0120] dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdimethyl,

[0121]dimethylsilyl-bis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene,

[0122] dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

[0123] dimethylsilyl-bis(tetrahydroindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,di(isopropylamino)borandiylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl,

[0124] dimethylsilyl-bis(tetrahydrofluorenyl)zirconiumbis(trimethylsilyl),(isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl, and

[0125] dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconiumdimethyl.

[0126] A further class of metal complexes utilized in the presentinvention corresponds to the preceding formula Lp₁MX_(m)X′_(n)X″_(p), ora dimer thereof, wherein X is a divalent group of up to 50 non-hydrogenatoms that together with Lp forms a metallocycle with M.

[0127] Preferred divalent X groups include groups containing up to 30non-hydrogen atoms comprising at least one atom that is oxygen, sulfur,boron or a member of Group 14 of the Periodic Table of the Elementsdirectly attached to the delocalized π-bonded group, and a differentatom, selected from the group consisting of nitrogen, phosphorus, oxygenor sulfur that is covalently bonded to M.

[0128] A preferred class of such Group 4 metal coordination complexesused according to the present invention corresponds to the formula:

[0129] wherein,

[0130] M is titanium or zirconium, preferably titanium in the +2, +3, or+4 formal oxidation state;

[0131] R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system,

[0132] each X″ is a halo, hydrocarbyl, hydrocarbyloxy or silyl group,said group having up to 20 non-hydrogen atoms, or two X″ groups togetherform a neutral C₅₋₃₀ conjugated diene or a divalent derivative thereof;

[0133] Y is —O—, —S—, —NR*—, —PR*—; and

[0134] Z is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*=CR*, CR*₂SiR*₂,GeR*₂, or B(NR**₂) wherein R* and R** are as previously defined.

[0135] Illustrative Group 4 metal complexes of the latter formula thatmay be employed in the practice of the present invention include:

[0136] cyclopentadienyltitaniumtrimethyl,

[0137] indenyltitaniumtrimethyl,

[0138] octahydrofluorenyltitaniumtrimethyl,

[0139] tetrahydroindenyltitaniumtrimethyl,

[0140] tetrahydrofluorenyltitaniumtrimethyl,

[0141](tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η⁵-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,

[0142](tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η⁵-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,

[0143] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium dibenzyl,

[0144](tert-butylamido)(tetramethyld-η⁵-cyclopentadienyl)dimethylsilanetitaniumdimethyl,

[0145](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitaniumdimethyl,

[0146] (tert-butylamido)(tetramethyl-η⁵-indenyl)dimethylsilanetitaniumdimethyl,

[0147] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III) 2-(dimethylamino)benzyl;

[0148](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III) allyl,

[0149](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III) 2,4-dimethylpentadienyl,

[0150](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0151](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 1,3-pentadiene,

[0152] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,

[0153] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)2,4-hexadiene,

[0154] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)2,3-dimethyl-1,3-butadiene,

[0155] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (I)isoprene,

[0156] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)1,3-butadiene,

[0157] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)2,3-dimethyl-1,3-butadiene,

[0158] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)isoprene

[0159] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanum (IV)dimethyl

[0160] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)dibenzyl

[0161] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)1,3-butadiene,

[0162] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II)1,3-pentadiene,

[0163] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II),4-diphenyl-1,3-butadiene,

[0164] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)1,3-pentadiene,

[0165] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)dimethyl,

[0166] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)dibenzyl,

[0167] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0168] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene,

[0169] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 2,4-hexadiene,

[0170](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(IV) 1,3-butadiene,

[0171](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene,

[0172](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(IV) isoprene,

[0173](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(II) 1,4-dibenzyl-1,3-butadiene,

[0174](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 2,4-hexadiene,

[0175](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(II) 3-methyl-1,3-pentadiene,

[0176] (tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl,

[0177](tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitaniumdimethyl,

[0178](tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,

[0179](tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl

[0180] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienylmethylphenylsilanetitanium (IV) dimethyl,

[0181] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienylmethylphenylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,

[0182]1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyltitanium(IV) dimethyl,

[0183] 1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyltitanium (II) 1,4-diphenyl-1,3-butadiene,

[0184] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene,

[0185] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV) isoprene

[0186] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV) dimethyl

[0187] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV) dibenzyl

[0188] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(IV) 1,3-butadiene,

[0189] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(II)1,3-pentadiene,

[0190] (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene, and

[0191](tert-butylamido)(3-N-pyrrolidinylinden-1-yl)dimethylsilanetitanium (IV)dimethyl.

[0192] Other catalysts, especially catalysts containing other Group 4metals, will, of course, be apparent to those skilled in the art. Mosthighly preferred metal complexes for use herein are the following metalcomplexes:

[0193] (t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitaniumdimethyl,

[0194] (t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II) 1,3-pentadiene,

[0195] (t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,

[0196](cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitaniumdimethyl,

[0197]cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II)1,3-pentadiene,

[0198]cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II)1,4 diphenyl-1,3-butadiene,

[0199](cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitaniumdimethyl,

[0200](cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II) 1,3-pentadiene,

[0201](cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,

[0202] (t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitaniumdimethyl,

[0203] (t-butylamido) dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II) 1,3-pentadiene,

[0204] (t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(1I) 1,4 diphenyl-1,3-butadiene,

[0205] (cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitaniumdimethyl,

[0206] cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(11)1,3-pentadiene,

[0207]cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II) 1,4diphenyl-1,3-butadiene,

[0208](cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitaniumdimethyl,

[0209](cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II)1,3-pentadiene,

[0210](cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0211](t-butylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitaniumdimethyl,

[0212](t-butylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitanium(II)1,3-pentadiene,

[0213](t-butylamido)dimethyl(3,4-(cyclopenta(l)penanthren-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0214](cyclohexylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitaniumdimethyl,

[0215]cyclohexylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitanium(II)1,3-pentadiene,

[0216] cyclohexylamido)dimethyl(3,4-(cyclopenta(l)phenanthren1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,

[0217](cyclododecylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitaniumdimethyl,

[0218](cyclododecylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitanium(II)1,3-pentadiene,

[0219](cyclododecylamido)dimethyl(3,4-(cyclopenta(l)phenanthren-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0220] (t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

[0221](t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

[0222](t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0223](cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

[0224]cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

[0225]cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0226](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

[0227](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

[0228](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0229] (t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

[0230] (t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,3-pentadiene,

[0231] (t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,

[0232](cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

[0233]cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

[0234]cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4 dipheney-1,3-butadiene,

[0235](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitaniumdimethyl,

[0236](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,3-pentadiene,

[0237](cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0238](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

[0239](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

[0240](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0241](cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

[0242]cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

[0243]cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0244](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

[0245](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

[0246](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0247](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

[0248](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium (II)1,3-pentadiene,

[0249](t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium (II)1,4 diphenyl-1,3-butadiene,

[0250](cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

[0251]cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

[0252]cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0253](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitaniumdimethyl,

[0254](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,3-pentadiene,

[0255](cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,

[0256] 1,2-ethanebis(inden-1-yl)zirconium dimethyl,

[0257] 1,2-ethanebis(inden-1-yl)zirconium(II) 1,3-pentadiene,

[0258] 1,2-ethanebis(inden-1-yl)zirconium(II) 1,4diphenyl-1,3-butadiene,

[0259] 1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium dimethyl,

[0260] 1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium(II)1,3-pentadiene,

[0261] 1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium(II) 1,4diphenyl-1,3-butadiene, dimethylsilanebis(inden-1-yl)zirconium dimethyl,

[0262] dimethylsilanebis(inden-1-yl)zirconium(II) 1,3-pentadiene,

[0263] dimethylsilanebis(inden-1-yl)zirconium(II) 1,4diphenyl-1,3-butadiene,

[0264] dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium dimethyl,

[0265] dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium(II)1,3-pentadiene, and

[0266] dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium(II) 1,4diphenyl-1,3-butadiene.

[0267] The cocatalysts of the invention may be, and preferably are usedin combination with an oligomeric or polymeric alumoxane compound, atri(hydrocarbyl)aluminum compound, adi(hydrocarbyl)(hydrocarbyloxy)aluminum compound, adi(hydrocarbyl)(dihydrocarbyl-amido)aluminum compound, abis(dihydrocarbyl-amido)(hydrocarbyl)aluminum compound, adi(hydrocarbyl)amido(disilyl)aluminum compound, adi(hydrocarbyl)-amido(hydrocarbyl)(silyl)aluminum compound, abis(dihydrocarbylamido)(silyl)aluminum compound, or a mixture of theforegoing compounds, having from 1 to 20 non-hydrogen atoms in eachhydrocarbyl, hydrocarbyloxy, or silyl group, if desired. These aluminumcompounds are usefully employed for their beneficial ability to scavengeimpurities such as oxygen, water, and aldehydes from the polymerizationmixture as well as to react with the hydroxyl group or quiescentreactive functionality of the compounds or the reactive derivativesthereof.

[0268] Preferred aluminum compounds include C₁₋₂₀ trialkyl aluminumcompounds, especially those wherein the alkyl groups are ethyl, propyl,isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl,dialkyl(aryloxy)aluminum compounds containing from 1-6 carbons in thealkyl group and from 6 to 18 carbons in the aryl group (especially(3,5-di(t-butyl)-4-methylphenoxy)diisobutylaluminum), methylalumoxane,modified methalumoxane, especially isobutyl modified alumoxane, andtri(ethylaluminum)-, tris(pentafluorophenyl)borane-, ortris(pentafluorophenyl)aluminum-modified alumoxanes or supportedderivatives thereof. (The latter compositions are previously known,having been disclosed in WO99/15534. Additional species include mixturesof aluminum containing Lewis acids as disclosed in U.S. Pat. No.6,214,760 and U.S. Pat. No. 6,211,111. The molar ratio of activator toaluminum compound is preferably from 1:10,000 to 1000:1, more preferablyfrom 1:5000 to 100:1, most preferably from 1:100 to 100:1.

[0269] The equivalent ratio of catalyst/cocatalyst (calculated based onquantity of metal in the catalyst and anionic charges on the cocatalyst)employed preferably ranges from 1:10 to 10:1, more preferably from 1:5to 2:1, most preferably from 1:4 to 1:1. Mixtures of the activatingcocatalysts of the present invention may also be employed if desired.

[0270] Suitable addition polymerizable monomers include ethylenicallyunsaturated monomers, acetylenic compounds, conjugated or non-conjugateddienes, and polyenes. Preferred monomers include olefins, for examplesalpha-olefins having from 2 to 20,000, preferably from 2 to 20, morepreferably from 2 to 8 carbon atoms and combinations of two or more ofsuch alpha-olefins. Particularly suitable alpha-olefins include, forexample, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene,1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, or combinationsthereof, as well as long chain vinyl terminated oligomeric or polymericreaction products formed during the polymerization, and C₁₀₋₃₀ α-olefinsspecifically added to the reaction mixture in order to producerelatively long chain branches in the resulting polymers. Preferably,the alpha-olefins are ethylene, propene, 1-butene, 4-methyl-pentene-1,1-hexene, 1-octene, and combinations of ethylene and/or propene with oneor more of such other alpha-olefins. Other preferred monomers includestyrene, halo- or alkyl substituted styrenes, vinylbenzocyclobutene,1,4-hexadiene, dicyclopentadiene, ethylidene norbomene, and1,7-octadiene. Mixtures of the above-mentioned monomers may also beemployed.

[0271] In general, the polymerization may be accomplished at conditionswell known in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions. Suspension, solution, slurry, gas phase orhigh pressure, whether employed in batch or continuous form or otherprocess conditions, may be employed if desired. Examples of such wellknown polymerization processes are depicted in WO 88/02009, U.S. Pat.Nos. 5,084,534, 5,405,922, 4,588,790, 5,032,652, 4,543,399, 4,564,647,4,522,987, and elsewhere. Preferred polymerization temperatures are from0-250° C. Preferred polymerization pressures are from atmospheric to3000 atmospheres.

[0272] Suitable processing conditions include solution polymerization,more preferably continuous solution polymerization processes, conductedin the presence of an aliphatic or alicyclic liquid diluent, preferablyusing the unsupported, quiescent reactive functionality containingcompounds. By the term “continuous polymerization” is meant that atleast the products of the polymerization are continuously removed fromthe reaction mixture, such as for example by devolatilization of aportion of the reaction mixture. Preferably one or more reactants arealso continuously added to the polymerization mixture during thepolymerization. Examples of suitable aliphatic or alicyclic liquiddiluents include straight and branched-chain C₄₋₁₂ hydrocarbons andmixtures thereof; alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof, and perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, and the like. Suitable diluents also include aromatichydrocarbons (particularly for use with aromatic a-olefins such asstyrene or ring alkyl-substituted styrenes) including toluene,ethylbenzene or xylene, as well as liquid olefins (which may act asmonomers or comonomers) including ethylene, propylene, butadiene,cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene,allylbenzene, vinyltoluene (including all isomers alone or inadmixture), and the like. Mixtures of the foregoing are also suitable.The foregoing diluents may also be advantageously employed during thesynthesis of the metal complexes and catalyst activators of the presentinvention.

[0273] In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 0.1:1, morepreferably from 10⁻¹²:1 to 10⁻⁵:1.

[0274] The catalyst composition of the invention may also be utilized incombination with at least one additional homogeneous or heterogeneouspolymerization catalyst in the same reactor or in separate reactorsconnected in series or in parallel to prepare polymer blends havingdesirable properties.

[0275] Molecular weight control agents can be used in combination withthe present cocatalysts. Examples of such molecular weight controlagents include hydrogen, trialkyl aluminum compounds or other knownchain transfer agents. A particular benefit of the use of the presentcocatalysts is the ability (depending on reaction conditions) to producenarrow molecular weight distribution cc-olefin homopolymers andcopolymers in greatly improved catalyst efficiencies. Preferred polymershave Mw/Mn of less than 2.5, more preferably less than 2.3. Such narrowmolecular weight distribution polymer products are highly desirable dueto improved tensile strength properties.

[0276] The catalyst composition of the present invention can also beemployed to advantage in the gas phase polymerization andcopolymerization of olefins. Gas phase processes for the polymerizationof olefins, especially the homopolymerization and copolymerization ofethylene and propylene, and the copolymerization of ethylene with higheralpha olefins such as, for example, 1-butene, 1-hexene,4-methyl-1-pentene are well known in the art. Such processes are usedcommercially on a large scale for the manufacture of high densitypolyethylene (HDPE), medium density polyethylene (MDPE), linear lowdensity polyethylene (LLDPE) and polypropylene.

[0277] The gas phase process employed can be, for example, of the typewhich employs a mechanically stirred bed or a gas fluidized bed as thepolymerization reaction zone. Preferred is the process wherein thepolymerization reaction is carried out in a vertical cylindricalpolymerization reactor containing a fluidized bed of polymer particlessupported above a perforated plate, the fluidisation grid, by a flow offluidisation gas.

[0278] The gas employed to fluidize the bed comprises the monomer ormonomers to be polymerized, and also serves as a heat exchange medium toremove the heat of reaction from the bed. The hot gases emerge from thetop of the reactor, normally via a tranquilization zone, also known as avelocity reduction zone, having a wider diameter than the fluidized bedand wherein fine particles entrained in the gas stream have anopportunity to gravitate back into the bed. It can also be advantageousto use a cyclone to remove ultra-fine particles from the hot gas stream.The gas is then normally recycled to the bed by means of a blower orcompressor and one or more heat exchangers to strip the gas of the heatof polymerization.

[0279] A preferred method of cooling of the bed, in addition to thecooling provided by the cooled recycle gas, is to feed a volatile liquidto the bed to provide an evaporative cooling effect. The volatile liquidemployed in this case can be, for example, a volatile inert liquid, forexample, a saturated hydrocarbon having 3 to 8, preferably 4 to 6,carbon atoms. In the case that the monomer or comonomer itself is avolatile liquid, or can be condensed to provide such a liquid this canbe suitably be fed to the bed to provide an evaporative cooling effect.Examples of olefin monomers which can be employed in this manner areolefins containing from 3 to 8, preferably from 3 to 6 carbon atoms. Thevolatile liquid evaporates in the hot fluidized bed to form gas whichmixes with the fluidizing gas. If the volatile liquid is a monomer orcomonomer, it will undergo some polymerization in the bed. Theevaporated liquid then emerges from the reactor as part of the hotrecycle gas, and enters the compression/heat exchange part of therecycle loop. The recycle gas is cooled in the heat exchanger and, ifthe temperature to which the gas is cooled is below the dew point,liquid will precipitate from the gas. This liquid is desirably recycledcontinuously to the fluidized bed. It is possible to recycle theprecipitated liquid to the bed as liquid droplets carried in the recyclegas stream, as described, for example, in EP-A-89691, U.S. Pat. No.4,543,399, WO 94/25495 and U.S. Pat. No. 5,352,749. A particularlypreferred method of recycling the liquid to the bed is to separate theliquid from the recycle gas stream and to reinject this liquid directlyinto the bed, preferably using a method which generates fine droplets ofthe liquid within the bed.

[0280] The polymerization reaction occurring in the gas fluidized bed iscatalyzed by the continuous or semi-continuous addition of catalyst.Such catalyst can be supported on an inorganic or organic supportmaterial if desired. Direct addition of the catalyst in the form of asolution in a solvent to a gas-phase polymerization reactor may beemployed as well. The catalyst can also be subjected to aprepolymerization step, for example, by polymerizing a small quantity ofolefin monomer in a liquid inert diluent, to provide a catalystcomposite comprising catalyst particles embedded in olefin polymerparticles.

[0281] The polymer is produced directly in the fluidized bed bycatalyzed (co)polymerization of the monomer(s) on the fluidizedparticles of catalyst, supported catalyst or prepolymer within the bed.Start-up of the polymerization reaction is achieved using a bed ofpreformed polymer particles, which, preferably, is similar to the targetpolyolefin, and conditioning the bed by drying with inert gas ornitrogen prior to introducing the catalyst, the monomer(s) and any othergases which it is desired to have in the recycle gas stream, such as adiluent gas, hydrogen chain transfer agent, or an inert condensable gaswhen operating in gas phase condensing mode. The produced polymer isdischarged continuously or discontinuously from the fluidized bed asdesired, optionally exposed to a catalyst kill and optionallypelletized.

[0282] Slurry polymerization conditions and supported catalystpreparation techniques for use therein are well known from the publishedliterature. Generally such catalysts are prepared by the same techniquesas are employed for making supported catalysts used in gas phasepolymerizations. Slurry polymerization conditions generally encompasspolymerization of a C₂₋₂₀ olefin, diolefin, cycloolefin, or mixturethereof in an aliphatic solvent at a temperature below that at which thepolymer is readily soluble in the presence of a supported catalyst.Slurry phase processes particularly suited for the polymerization ofC₂₋₆ olefins, especially the homopolymerization and copolymerization ofethylene and propylene, and the copolymerization of ethylene with C₃₋₈α-olefins such as, for example, 1-butene, 1-hexene, 4-methyl-1-penteneand 1-octene are well known in the art. Such processes are usedcommercially on a large scale for the manufacture of high densitypolyethylene (HDPE), medium density polyethylene (MDPE), linear lowdensity polyethylene (LLDPE) and polypropylene, especially isotacticpolypropylene.

[0283] In addition to the foregoing techniques for coordination additionpolymerizations, the present compounds and compositions disclosed hereinare useful as initiators or catalysts in the field of cationicpolymerization. Preferred monomers for such cationic polymerizationsinclude styrene, α-methylstyrene, ring alkyl-substituted styrene,isobutylene, and mixtures thereof. Preferred temperatures for cationicpolymerizations are from −100 to 50° C., preferably −80 to 20° C.

EXAMPLES

[0284] It is understood that the present invention is operable in theabsence of any component which has not been specifically disclosed. Thefollowing examples are provided in order to further illustrate theinvention and are not to be construed as limiting. Unless stated to thecontrary, all parts and percentages are expressed on a weight basis. Theterm “overnight”, if used, refers to a time of approximately 16-18hours, “room temperature”, if used, refers to a temperature of 20-25°C., and “mixed alkanes” refers to a mixture of mostly C₆-C₁₂ alkanesavailable commercially under the trademark Isopar E™ from ExxonChemicals Inc.

[0285] All manipulation of air sensitive materials was performed in anargon filled, vacuum atmospheres, glove box or on a high vacuum lineusing standard Shlenk techniques. Toluene was purified by passagethrough columns packed with activated alumina (Kaiser A-2) and supportedcopper (Engelhard, Cu-0224 S). Hexanes were purified by distillationfrom sodium benzophenone ketyl. Tris(pentafluorophenyl)borane (FAB) waspurchased from Boulder Scientific. Dioctadecylmethylamine is abis(hydrogenated tallow) alkylamine of approximate formulation(C₁₈H₃₅)₂CH₃N, available commercially under the tradename Armeen™ M2HTfrom Akzo Nobel, Inc., and was used as received.

Example 1 [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{(C₁₇H₃₃C(O)O)[B(C₆F₅)₃]₂}⁻

[0286] A) Synthesis of [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺[(C₁₇H₃₃C(O)O]⁻

[0287] To a flask containing 533 mg (1.87 mmol) of stearic acid 1000 mg(1.87 mmol) of Armeen™ M2HT and 25 g of hexane were added. The reactionmixture was warmed until a clear solution resulted. After 30 minutes ofstirring the volatiles were removed under vacuum, leaving the desiredproduct as a white solid.

[0288] B) Synthesis of[H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{(C₁₇H₃₃C(O)O)[B(C6F₅)₃]₂}⁻

[0289] A flask containing FAB (123 mg, 0.24 mmol) and 20 ml of toluenewas charged with 99 mg (0.12 mmol) of the ammonium stearate saltprepared in step A). A clear, 0.006 molar solution of the desiredcomplex for use in polymerization resulted.

Example 2

[0290] The reaction conditions of Example 1 were substantially repeated,excepting that the ammonium stearate salt was not isolated beforeaddition of 2 equivalents of FAB. A clear, toluene solution of thedesired product resulted. Example 3

[H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{NO₃[B(C₆F₅)₃]₂}⁻

[0291] A) Synthesis of [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺[NO₃]⁻

[0292] To a flask containing 277 mg of silver nitrate suspended in 35 ghexane, 932 mg of the hydrochloride salt of Armeen™ M2HT were added. Themixture was heated to 40° C. for 15 minutes, cooled to room temperatureand sonicated for 2 hours, then stirred an additional 48 hours. Thereaction mixture was warmed again to 40° C. and filtered through a padof diatomaceous earth. The filtrate containing the desired product wasretained.

[0293] B) Synthesis of [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{(NO₃)[B(C₆F₅)₃]₂}⁻

[0294] FAB (2.5 g, 4.8 mmol) was added to the filtrate obtained fromstep A). After 1 hour, all volatiles were removed under reducedpressure. The resulting product was redissolved in toluene to give aclear, 0.006 M solution of the desired product for use inpolymerization.

Example 4 [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{C(C(O)CH₃)₃[B(C₆F₅)₃]₃}⁻

[0295] Methyl triacetyl (HC(C(O)CH₃)₃, 17 mg, 0.13 mmoles) and Armeen™M2HT ((C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N, 64 mg, 0.13 mmoles) were combined in 10 mlof toluene. After 15 minutes, FAB, (6.082 g of a 3.03 weight percentsolution in mixed alkanes, 0.36 mmole) was added. After 10 minutesstirring another 1.0 ml of toluene was added to give a 0.006 molarsolution which was used as a polymerization catalyst solution withoutfurther modification.

Example 5 [H(C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N]⁺{C₉O₂H₅[B(C₆F₅)₃]₂}⁻

[0296] Indan-1,3-dione (C₉O₂H₆, 17 mg, 0.12 mmoles) and Armeen™ M2HT((C₁₄₋₁₈H₂₇₋₃₅)₂(CH₃)N, 64 mg, 0.13 mmoles) were combined in 10 ml oftoluene. After 15 minutes, FAB, (4.055 g of a 3.03 weight percentsolution in mixed alkanes, 0.24 mmole) was added. After 10 minutesstirring another 4.2 ml of toluene was added to give a 0.006 molarsolution which was used as a polymerization catalyst solution withoutfurther modification.

[0297] Polymerizations

[0298] Mixed alkanes and liquid olefins are purified by sparging withpurified nitrogen followed by passage through columns containing alumina(A-2, available from LaRoche Inc.) and Q5 reactant (available fromEnglehard Chemicals Inc.) at 50 psig (450 kPa) using a purified nitrogenpad. All transfers of solvents and solutions described below areaccomplished using a gaseous pad of dry, purified nitrogen or argon.Gaseous feeds to the reactor are purified by passage through columns ofA-204 alumina (available from LaRoche Inc.) and Q5 reactant. Thealuminas are previously activated by treatment at 375° C. with nitrogen,and Q5 reactant is activated by treatment at 200° C. with 5 percenthydrogen in nitrogen.

[0299] A stirred, two-liter Parr reactor was charged with approximately433 g of toluene and 455 g of 1-octene comonomer. Hydrogen was added asa molecular weight control agent by differential pressure expansion froma 75 mL addition tank at 50 psig (450 kPa). The reactor was heated to90° C. and saturated with ethylene at 200 psig (1.4 MPa). Theappropriate amount of catalyst,tetramethylcyclopentadienyl)dimethyl(t-butylamido)silane titanium (II)1,3-pentadiene and cocatalyst (either an example of the invention or acomparative cocatalyst, dioctadecylmethylammoniumtetrakis(pentafluorophenyl)borate, DAB) in toluene were premixed in aglovebox in a 1:1.1 molar ratio and transferred to a catalyst additiontank and injected into the ;t reactor. (Periodic additions ofcatalyst/cocatalyst solution may be added during the course of the run.)The polymerization conditions were maintained during the run withethylene on demand.

[0300] The resulting solution was removed from the reactor into anitrogen purged collection vessel containing 100 ml of isopropyl alcoholand 20 ml of a 10 weight percent toluene solution of hindered phenolantioxidant (Irganox™ 1010 from Ciba Geigy Corporation) and phosphorusstabilizer (Irgafos™ 168 from Ciba Geigy Corporation). Polymers formedare dried in a programmed vacuum oven with a maximum temperature of 140°C. and a 20 hour heating period. Results of the polymerization arereported in Table 1. TABLE 1 Run Cocatalyst Max C₂H₄ flow (g/min)Efficiency²  1* DAB¹ 31.8 1.8  2* ″ 31.8 1.8  3 Ex. 1 39.3 2.7  4 ″ 31.82.4  5* DAB 24.9 1.8  6* ″ 27.8 —  7 Ex. 3 30.7 —  8 ″ 19.2 —  9* DAB24.7 — 10* ″ 14.8 1.5 11 Ex. 4 23.7 1.6 12 ″ 26.2 1.7 13 Ex. 5 30.6 2.014 ″ 30.1 2.0 15* DAB 13.4 1.3

What is claimed is:
 1. A compound corresponding to the formula:(A*^(+a))_(b)(Z*J*_(j))^(−c) _(d), wherein: A* is a proton or a cationof from 1 to 80 atoms, preferably 1 to 60 atoms, not counting hydrogenatoms, said A* having a charge+a; Z* is an anion group of from 1 to 50atoms, preferably 1 to 30 atoms, not counting hydrogen atoms, furthercontaining two or more Lewis base sites, said Z* being the conjugatebase of an inorganic Bronsted acid or a carbonyl- or non-cyclic,imino-group containing organic Bronsted acid; J* independently eachoccurrence is a Lewis acid of from 1 to 80 atoms, preferably 1 to 60atoms, not counting hydrogen atoms, coordinated to at least one Lewisbase site of Z*, and optionally two or more such J* groups may be joinedtogether in a moiety having multiple Lewis acidic functionality; j is anumber from 1 to 12; and a, b, c, and d are integers from 1 to 3, withthe proviso that a×b is equal to c×d.
 2. A compound according to claim 1wherein Z* is selected from the group consisting of: NO₃ ⁻, PO₄ ³⁻, SO₄²⁻, RSO₃ ⁻, CO₃ ²⁻, [RC(O)O], [RC(NR)NR], [R′C(O)CR′C(O)R′]⁻,[(R′C(O))₃C]⁻, [RC(NR)CRC(NR)R]⁻, and [(RC(NR))₃C]⁻, wherein each R isindependently a hydrogen-; hydrocarbyl-; or halocarbyl-group; ahydrocarbyl group further substituted with one or more carbonyl-, halo-,hydroxy-, dialkylamino-, dialkylaluminumoxy-, trihydrocarbylsilyl-,trihydrocarbylsiloxy-, or hydrocarbyloxy-groups; or a halocarbyl groupfurther substituted with one or more carbonyl-, hydroxy-, dialkylamino-,dialkylaluminumoxy-, trihydrocarbylsilyl-, trihydrocarbylsiloxy-, orhydrocarbyloxy-groups; and each R′ is independently R or two R′ groupsmay be joined together thereby forming a divalent group.
 3. A compoundaccording to claim 3 wherein Z* is an acetylacetonate,cyclohexa-1,3-dionate, [RC(O)O]⁻ or NO₃ ⁻², wherein R is a C₆₋₂₄hydrocarbyl group, most preferably a C₁₂₋₂₄ alkyl group, or anindane-1,3-dione anion or methyl triacetyl anion of the followingstructure:


4. A compound according to claim 1 wherein A*^(+a) is a proton or isselected from the group consisting of ammonium, sulfonium, phosphonium,oxonium, carbonium, silylium, ferrocenium, Ag⁺, and Pb⁺² cations.
 5. Acompound according to claim 1 wherein A*^(+a) is a trimethylammonium-,triethylammonium-, tripropylammonium-, tri(n-butyl)ammonium-,methyldi(C₁₄₋₁₈ alkyl)ammonium-, dimethyl(C₁₄₋₁₈ alkyl)ammonium-,N,N-dimethylanilinium-, N,N-diethylanilinium-,N,N-dimethyl(2,4,6-trimethylanilinium)-, N,N-di(tetradecyl)lanilinium-,N,N-di(tetradecyl)-2,4,6-trimethylanilinium)-,N,N-di(octadecyl)lanilinium-,N,N-di(octadecyl)-2,4,6-trimethylanilinium)-, ormethyldicyclohexylammonium-cation.
 6. A compound according to claim 1wherein J*′ is tris(pentafluorophenyl)borane ortris(pentafluorophenyl)alumane).
 7. A compound according to claim 1 thatis a bis(tris(pentafluorophenyl)borane)-coordinated derivative of atrihydrocarbylammonium stearate or amono(tris(pentafluorophenyl)-borane)-coordinated derivative of atrihydrocarbylammonium stearate.
 8. A composition of matter comprising acompound according to any one of claims 1-7 and an organoaluminumcompound, preferably an alumoxane.
 9. A composition of matter comprisingthe admixture or reaction product, optionally in an inert diluent, of aninorganic Bronsted acid or a carbonyl- or non-cyclic,imino-group-containing organic Bronsted acid; from one to twelve molesper mole of Bronsted acid of a Lewis acid of from 1 to 80, preferably 1to 60 atoms, not counting hydrogen atoms; optionally an amine orphosphine containing Lewis base of from 1 to 80, preferably 1 to 60atoms, not counting hydrogen; and further optionally an organoaluminumcompound.
 10. A catalyst composition for polymerization of additionpolymerizable monomers comprising the combination or reaction productresulting from combining, 1) a Group 3-10 or Lanthanide metal complex,preferably a Group 4 metal complex, 2) a compound according to any oneof claims 1-7, 3) optionally an organoaluminum compound, preferably analumoxane, and further optionally 4) a solid, particulated support. 11.A catalyst composition for polymerization of addition polymerizablemonomers comprising the combination or reaction product resulting fromcombining, 1) a Group 3-10 or Lanthanide metal complex, preferably aGroup 4 metal complex, 2) a compound according to claim 8, andoptionally 3) a solid, particulated support.
 12. A polymerizationprocess comprising contacting one or more α-olefins under polymerizationconditions with a catalyst composition according to claim
 10. 13. Apolymerization process according to claim 12 that is a solutionpolymerization.
 14. A polymerization process according to claim 12 thatis a gas phase polymerization.
 15. A polymerization process according toclaim 12 that is a slurry polymerization.
 16. A polymerization processaccording to claim 12 that is a cationic polymerization.
 17. Apolymerization process comprising contacting one or more α-olefins underpolymerization conditions with a catalyst composition according to claim11.
 18. A polymerization process according to claim 17 that is asolution polymerization.
 19. A polymerization process according to claim17 that is a gas phase polymerization.
 20. A polymerization processaccording to claim 17 that is a slurry polymerization.
 21. Apolymerization process according to claim 17 that is a cationicpolymerization.